Supporting information. Palladium nanoparticles generated in situ used as catalysts in carbonylative cross-coupling in aqueous medium

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting information Palladium nanoparticles generated in situ used as catalysts in carbonylative cross-coupling in aqueous medium P. Wójcik a, M. Mart b, S. Ulukanli b, A.M. Trzeciak a* a University of Wrocław, Faculty of Chemistry, 14 F. Joliot-Curie, Wrocław, Poland b Department of Chemistry, Faculty of Science and Letters, Osmaniye Korkut Ata University, Osmaniye, Turkey * corresponding author, anna.trzeciak@chem.uni.wroc.pl 1. Synthesis of palladium complexes Imidazole (2 x 10-3 mol) and CH 3 CN (10 ml) were added to PdCl 2 (cod) (1 x 10-3 mol), and the solution was heated for 2.5 h at 70 o C. After cooling down to ambient temperature, the solution was concentrated in vacuo. The product was filtered off, washed with CH 3 CN, Et 2 O, and dried in vacuo. Pd(1-MI) 2 Cl 2 (Yield: 80%) Anal. Calc. for C 8 H 12 N 4 Cl 2 Pd: C 28.13; H 3.54; N Found: C 27.99; H 3.51; N H NMR (500 MHz, CDCl 3 ): δ (ppm): 3.66 (3H, s, NCH 3 ); 6.74 (1H d, J H-H = 1.7 Hz, CH); 7.38 (1H d, J H-H = 1.7 Hz, CH); 7.95 (1H, s, N 2 CH). 13 C NMR (125 MHz, CDCl 3 ): δ (ppm): 34.6 (NCH 3 ); (CH); (CH), (N 2 C). Pd(1-BI) 2 Cl 2 (Yield: 65%) Anal. Calc. for C 14 H 24 N 4 Cl 2 Pd: C 39.50; H 5.68; N Found: C 39.75; H 5.69; N H NMR (500 MHz, CDCl 3 ): δ (ppm): 0.92 ppm (3H, t, J H-H = 7.4 Hz, CH 3 ); 1.30 ppm (2H, sx, J H-H = 7.4 Hz, CH 2 ); 1.72 (2H, q, J H-H = 7.4 Hz, CH 2 ), 3.87 (2H, t, J H-H = 7.4 Hz, NCH 2 ); 6.75 (1H, s, CH); 7.38 (1H, s, CH); 7.97 (1H, s, CH). 13 C NMR (125 MHz, CDCl 3 ): δ (ppm): 13.4 (CH 3 ); 19.6 (CH 2 ); 32.5 (CH 2 ); 48.1 (N-CH 2 ); (CH); (CH); (N 2 C). Table S1. Carbonylative Suzuki coupling of iodobenzene: testing solvent and base a Entry Solvent Base Conv. b (%) 1 b (%) 2 b (%) Selectivity to 1 (%) 1 IPA:water (1:1) KOH IPA:water (1:1) K 2 CO IPA:water (1:1) CsCO IPA:water (1:1) KH 2 PO IPA:water (1:1) NEt IPA:water (1:1) NEt(i-Pr) Anisole K 2 CO Ethylene glycol K 2 CO THF K 2 CO

2 10 Dioxane K 2 CO Ethanol K 2 CO Water NEt Water K 2 CO Water Na 2 CO a Pd(1-MI) 2 Cl 2 (1 mol %), base (3 mmol), solvent (5 ml), iodobenzene (1 mmol), phenyl boronic acid (1.2 mmol), CO (1atm), 60 o C, 2h. b Conversions were determined by GC using mesitylene as internal standard. IPA = 2-propanol Structural data of diarylketones (references S1 S19) O Benzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 4H), (m, 2H), (m, 4H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.9, 137.7, GC-MS: m/z = 51 (11%), 77 (42%), 105 (100%), 182 ([M + ] = 42%). O OMe 3-Methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), (m, 1H), (m, 2H), (m, 3H), 7.11 (ddd, J H-H = 7.8 Hz, 2.7 Hz, 1.5 Hz, 1H), 3.85 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.7, 159.8, 139.1, 137.8, 132.6, 130.2, 129.4, 128.5, 123.1, 119.1, 114.5, GC-MS: m/z = 51 (36%), 64 (21%), 77 (82%), 105 (96%), 135 (100%), 181 (18%), 212 ([M + ] = 82%). O MeO 4-Methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.81 (m, 2H), (m, 2H), 7.54 (t, J H-H = 7.4 Hz, 1H), 7.45 (t, J H-H = 7.4 Hz, 2H), (m, 2H), 3.87 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 195.7, 163.4, 138.5, 132.7, 132.1, 130.4, 129.9, 128.4, 113.7, GC- MS: m/z = 51 (25%), 64 (18%), 77 (89%), 105 (36%), 135 (100%), 212 ([M + ] = 82%).

3 OMe O 2-Methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), (m, 1H), (m, 3H), 7.34 (dd, J H-H = 7.4 Hz, 1.7 Hz, 1H), 7.02 (td, J H-H =7.5 Hz, 0.9 Hz, 1H), 6.98 (d, J H-H = 8.4 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.6, 157.5, 138.0, 133.1, 132.0, 130.0, 129.8, 129.1, 128.4, 120.7, 111.7, GC-MS: m/z = 51 (36%), 64 (21%), 77 (82%), 105 (96%), 135 (100%), 181 (18%), 212 ([M + ] = 82%). O 1-Naphthyl phenylketone: 1 H NMR (500 MHz, CDCl 3 ): δ 8.09 (d, J H-H = 8.2 Hz, 1H), 7.99 (d, J H-H = 8.2 Hz, 1H), 7.91 (d, J H-H = 8.2 Hz, 1H), 7.86 (d, J H-H = 7.8 Hz, 2H), (m, 2H), (m, 3H), 7.44 (t, J H-H = 7.8 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ): δ 198.2, 138.5, 136.5, 133.9, 133.4, 131.4, 131.1, 130.6, 128.6, 127.9, 127.4, 126.6, 125.9, GC-MS: m/z = 51 (25%), 77 (75%), 105 (71%), 127 (79%), 155 (100%), 232 ([M + ] = 97%). Spectral data are consistent with data reported in the literature. [ j, s, k] O S 2-Benzoylthiophene: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), 7.70 (dd, J H-H = 4.9 Hz, 1.1 Hz, 1H), 7.63 (dd, J H-H = 3.8 Hz, 1.1 Hz, 1H), (m, 1H), (m, 2H), 7.14 (dd, J H-H = 4.9 Hz, 3.8 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ): δ 188.4, 143.9, 138.4, 135.0, 134.4, 132.5, 129.4, 128.6, GC-MS: m/z = 39 (21%), 51 (21%), 77 (43%), 111 (100%), 188 ([M + ] = 61%). O O 1-Phthalanone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.91 (d, J H-H = 7.7 Hz, 1H), 7.67 (dt, J H-H = 7.5 Hz, 1.0 Hz, 1H), 7.51 (t, J H-H = 7.5 Hz, 1H), 7.47 (dt, J H-H = 7.7 Hz, 0.8 Hz, 1H), 5.31 (s, 2H). 13 C NMR (125 MHz, CDCl 3 ): δ 171.3, 146.7, 134.2, 129.2, 126.0, 125.9, 122.3, GC-MS: m/z = 51 (19%), 77 (53%), 105 (100%), 134 ([M + ] = 34%). O Br

4 4-Bromobenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), (m, 5H), (m, 2H). 13 C NMR (125 MHz, CDCl 3 ): δ 195.8, 137.4, 136.5, 132.9, 131.8, 131.7, 130.1, 128.6, GC-MS: m/z = 51 (21%), 77 (49%), 105 (100%), 155 (11%), 183 (32%), 260 and 262 ([M + ] = 19%). O Br 2-Bromobenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), 7.62 (d, J H-H = 8.0 Hz, 1H), 7.58 (t, J H-H = 7.4 Hz, 1H), 7.44 (t, J H-H = 7.8 Hz, 2H), (m, 1H), (m, 2H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.0, 140.9, 136.3, 133.9, 133.4, 131.3, 130.4, 129.2, 128.8, 127.4, GC-MS: m/z = 51 (29%), 77 (75%), 105 (100%), 155 (11%), 183 (28%), 260 and 262 ([M + ] = 28%) OMe O Br 2-Bromo-2'-methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.64 (dd, J H-H = 7.7 Hz, 1.8 Hz, 1H), 7.56 (d, J H-H = 7.6 Hz, 1H), (m, 1H), (m, 3H), 7.00 (t, J H-H = 7.5 Hz, 1H), 6.91 (d, J H-H = 8.3 Hz 1H), 3.63 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 195.4, 159.5, 142.9, 134.6, 133.2, 131.9, 131.1, 129.5, 127.4, 127.2, 120.9, 119.6, 112.2, GC-MS: m/z = 50 (11%), 63 (7%), 77 (39%), 92 (14%), 121 (14%), 135 (100%), 155 (11%), 183 (14%), 211 (25%), 290 and 292 ([M + ] = 11%). O Br MeO 2-Bromo-3'-methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.62 (d, J H-H = 8.0 Hz, 1H), (m, 2H), 7.33 (t, J H-H = 7.8 Hz, 3H), (m, 1H), 7.13 (dd, J H-H = 8.2 Hz, 2.3 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ): δ 195.8, 160.1, 140.9, 137.7, 133.4, 131.3, 129.8, 129.1, 127.3, 123.7, 120.7, 119.7, 113.9, GC-MS: m/z = 50 (8%), 64 (17%), 77 (35%), 92 (21%), 107 (33%), 135 (100%), 154 (19%), 183 (33%), 211 (96%), 290 and 292 ([M + ] = 23%). Spectral data are consistent with data reported in the literature. [d]

5 O Br MeO 2-Bromo-4'-methoxybenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.76 (d, J H-H = 9.0 Hz, 2H), (m, 1H), (m, 1H), (m, 2H), 6.91 (d, J H-H = 9.0 Hz, 2H), 3.85 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 194.6, 164.3, 141.3, 133.3, 132.8, 131.0, 129.3, 128.9, 127.4, 119.6, 114.1, GC-MS: m/z = 77 (18%), 92 (11%), 135 (100%), 290 and 292 ([M + ] = 18%). O Br 2-Bromo-4'-methylbenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.69 (d, J H-H = 8.2 Hz, 2H), (m, 1H), 7.38 (dt, J H-H = 7.6 Hz, 1.1 Hz, 1H), (m, 2H), 7.25 (d, J H-H = 7.9 Hz, 2H), 2.40 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 195.7, 145.0, 141.1, 133.8, 133.3, 131.1, 130.5, 129.5, 129.0, 127.3, 119.6, GC-MS: m/z = 65 (12%), 91 (36%), 119 (100%), 183 (6%), 274 and 276 ([M + ] = 36%). O Br S 2-(2-Bromobenzoyl)thiophene: 1 H NMR (500 MHz, CDCl 3 ): δ 7.74 (dd, J H-H = 4.9 Hz, 1.1 Hz, 1H), 7.63 (d, J H-H = 8.1 Hz, 1H), (m, 4H), 7.10 (dd, J H-H = 4.9 Hz, 3.8 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ): δ 188.0, 143.6, 140.6, 136.2, 135.9, 133.6, 131.5, 128.9, 128.5, 127.3, GC-MS: m/z = 39 (18%), 111 (100%), 154 (7%), 187 (11%), 266 and 268 ([M + ] = 14%). O Br 2-bromophenyl-1-naphthylketone: 1 H NMR (500 MHz, CDCl 3 ): δ 8.90 (d, J H-H = 8.6 Hz, 1H), 8.02 (d, J H-H = 8.2 Hz, 1H), 7.90 (d, J H-H = 8.2 Hz, 1H), (m, 2H), (m, 2H), 7.46 (dd, J H-H = 7.5 Hz, 1.7 Hz, 1H), (m, 2H), 7.34 (dt, J H-H = 7.6 Hz, 1.7 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ): δ 197.9, 142.2, 134.2, 134.1, 134.0, 133.6, 132.4, 131.7, 131.3, 130.2, 128.7, 128.6, 127.4, 126.9, 126.3, 124.5, GC-MS: m/z = 50 (7%), 75 (18%), 101 (29%), 127 (78%), 155 (96%), 183 (14%), 202 (14%), 231 (100%), 310 and 312 ([M + ] = 25%).

6 O O 1,4-Phenylenebis(phenyl)methanone: 1 H NMR (500 MHz, CDCl 3 ): δ 7.87 (s, 4H), (m, 4H), (m, 2H), 7.50 (t, J H-H = 7.7 Hz, 4H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.2, 140.9, 137.2, 133.2, 130.3, 130.0, GC-MS: m/z = 77 (48%), 105 (100%), 152 (8%), 181 (10%), 209 (48%) 286 ([M + ] = 36%). O O 4-Acetylbenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ 8.04 (d, J H-H = 8.5 Hz, 2H), 7.84 (d, J H-H = 8.5 Hz, 2H), (m, 2H), 7.60 (t, J H-H = 7.5 Hz, 1H), 7.48 (t, J H-H = 7.8 Hz, 2H), 2.65 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 197.7, 196.1, 141.5, , 133.2, 130.3, 130.2, 128.7, 128.4, GC-MS: m/z = 43 (28%), 51 (25%), 77 (75%), 105 (100%), 147 (36%), 209 (93%), 224 ([M + ] = 54%). O 4-Methylbenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), 7.70 (d, J H-H = 8.2 Hz, 2H), (m, 1H), (m, 2H), 7.26 (d, J H-H = 7.9 Hz, 2H), 2.43 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.7, 143.4, 138.2, 135.1, 132.4, 130.5, 130.1, 129.2, 128.4, GC-MS: m/z = 39 (11%), 51 (21%), 77 (50%), 91 (54%), 105 (57%), 119 (100%), 181 (14%), 196 ([M + ] = 64%). O (4-methylnaphthalen-1-yl)(phenyl)methanone: 1 H NMR (500 MHz, CDCl 3 ): δ 8.15 (d, J H-H = 8.3 Hz, 1H), 8.07 (d, J H-H = 8.3 Hz, 1H), (m, 2H), (m, 2H), (m, 4H), 7.34 (d, J H-H = 7.2 Hz, 1H), 2.76 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 198.3, 138.9, 138.5, 134.9, 133.2, 133.1, 131.3, 130.6, 128.6, 128.2, 127.1, 126.6, 126.5, 125.3, 124.6, GC-

7 MS: m/z =51 (12%), 77 (44%), 105 (25%), 115 (33%), 141 (37%), 169 (100%), 231 (23%), 246 ([M + ] = 60%). O 4-tert-Butylbenzophenone: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 4H), (m, 1H), (m, 4H), 1.35 (s, 9H). 13 C NMR (125 MHz, CDCl 3 ): δ 196.7, 156.4, 138.2, 135.0, 132.4, 130.3, 130.2, 128.4, 125.4, 35.3, GC-MS: m/z = 51 (11%), 77 (46%), 105 (68%), 161 (14%), 223 (100%), 238 ([M + ] = 39%). Structural data of benzoate esters (references S20 S25) O O Ethyl benzoate: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), (m, 1H), (m, 2H), 4.36 (q, J = 7.2 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 166.8, 133.0, 130.7, 129.7, 128.5, 61.1, GC-MS: m/z = 51 (18%), 77 (49%), 105 (100%), 122 (33%), 150 ([M + ] = 24%). O O Propyl benzoate: 1 H NMR (500 MHz, CDCl 3 ): δ 8.01 (d, J = 7.2 Hz, 2H), (m, 1H), (m, 2H), 5.23 (sept, J = 6.3 Hz, 1H), 1.35 (d, J = 6.3 Hz, 6H). 13 C NMR (125 MHz, CDCl 3 ): δ 166.3, 132.9, 131.1, 129.7, 128.5, 68.5, GC-MS: m/z = 51 (17%), 59 (20%), 77 (32%), 105 (100%), 123 (35%), 164 ([M + ] = 14%). O O

8 Methyl benzoate: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 2H), (m, 1H), (m, 2H), 3.90 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ): δ 167.3, 133.1, 130.4, 129.8, 128.5, GC-MS: m/z = 51 (24%), 77 (63%), 105 (100%), 136 (30%). References: S1. H. A. Reisch, V. Enkelmann, U. Scherf, J. Org. Chem., 64, 1999, S2. T. J. Korn, P. Knochel, Angew. Chem. Int. Ed., 44, 2005, S3. A. T. Biju, F. Glorius, Angew. Chem. Int. Ed., 49, 2010, S4. J. N. Moorthy, S. Samanta, J. Org. Chem., 72, 2007, S5. K. Kunchithapatham, Ch. C. Eichman, J. P. Stambuli, Chem. Commun., 47, 2011, S6. I. Sapountzis, W. Lin, Ch. C. Kofink, Ch. Despotopoulou, P. Knochel, Angew. Chem. Int. Ed., , S7. T. Ishiyama, H. Kizaki, T. Hayashi, A. Suzuki, N. Miyaura, J. Org. Chem., 63, 1998, S8. M. V. Khedkar, T. Sasakib, B. M. Bhanage, RSC Advances., 3, 2013, S9. M. V. Khedkar, P. J. Tambade, Z. S. Qureshi, B. M. Bhanage, Eur. J. Org. Chem., 2010, S10. D. Wang, Z. Zhang, Org. Lett., 5, 2003, S11. S. Zhu, Z. Zhang, X. Huang, H. Jiang, Z. Guo, Chem. Eur. J., 19, 2013, S12. P. J. Tambade, Y. P. Patil, A. G. Panda, B. M. Bhanage, Eur. J. Org. Chem., 2009, S13. H. Neumann, A. Brennführer, M. Beller, Chem. Eur. J., 14, 2008, S14. T. Morimoto, M. Fujioka, K. Fuji, K. Tsutsumi, K. Kakiuchi, J. Organomet. Chem., 692, 2007, S15. M. L. N. Rao, V. Venkatesh, D. Banerjee, Tetrahedron, 63, 2007, S16. M. J. Lo Fiego, M. A. Badajoz, G. F. Silbestri, M. T. Lockhart, A. B. Chopa, J. Org. Chem., , S17. Z. Zheng, J. Wen, N. Wang, B. Wu, X. Yu, Beilstein J. Org. Chem., 4, 2008, 40. S18. L. J. Gooßen, F. Rudolphi, Ch. Oppel, N. Rodriguez, Angew. Chem. Int. Ed. 47, 2008, S19. S. Karagöz, D. K. Astley, S. T. Astley Appl. Organomet. Chem. 14, 2000, S20. J-J. Kim, Y-D. Park, D-H. Kweon, Y-J. Kang, H-K. Kim, S.-G. Lee, S-D. Cho, W-S. Lee, Y-J. Yoon, Bull. Korean Chem. Soc. 25, 2004, S21. Q. Liu, Y. Lan, J. Liu, G. Li, Y-D. Wu, A. Lei, J. Am. Chem. Soc. 131, 2009, S22. Ch. Salome, H. Kohn, Tetrahedron 65, 2009, S23. Y. Hu, J. Liu, Z. Lu, X. Luo, H. Zhang, Y. Lan, A. Lei, J. Am. Chem. Soc. 132, 2010, S24. M. Hosseini-Sarvari, E. Sodagar, C. R. Chimie 16, 2013, S25. A. Schmidt, T. Habeck, B. Snovydovych, W. Eisfeld, Org. Lett., 9, 2007,

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